Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions
We report a 12-step catalytic enantioselective formal synthesis of malhamensilipin A (3) and diastereoisomeric analogues from (E)-2-undecenal. The convergent synthesis relied upon iterative epoxidation and phosphorus(V)-mediated deoxydichlorination reactions as well a titanium-mediated epoxide-openi...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Published: |
Royal Society of Chemistry
2016
|
| Online Access: | https://eprints.nottingham.ac.uk/35946/ |
| _version_ | 1848795195723743232 |
|---|---|
| author | Saska, J. Lewis, W. Paton, R.S. Denton, R.M. |
| author_facet | Saska, J. Lewis, W. Paton, R.S. Denton, R.M. |
| author_sort | Saska, J. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | We report a 12-step catalytic enantioselective formal synthesis of malhamensilipin A (3) and diastereoisomeric analogues from (E)-2-undecenal. The convergent synthesis relied upon iterative epoxidation and phosphorus(V)-mediated deoxydichlorination reactions as well a titanium-mediated epoxide-opening to construct the C11-C16 stereohexad. The latter transformation occurred with very high levels of stereoretention regardless of the C13 configuration of the parent epoxide, implicating anchimeric assistance of either the γ- or δ-chlorine atoms, and the formation of chloretanium or chlorolanium ions, respectively. A computational analysis of the chloronium ion intermediates provided support for the involvement of chlorolanium ions, whereas the potential chloretanium ions were found to be less likely intermediates on the basis of their greater carbocationic character |
| first_indexed | 2025-11-14T19:28:14Z |
| format | Article |
| id | nottingham-35946 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:28:14Z |
| publishDate | 2016 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-359462020-05-04T18:08:02Z https://eprints.nottingham.ac.uk/35946/ Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions Saska, J. Lewis, W. Paton, R.S. Denton, R.M. We report a 12-step catalytic enantioselective formal synthesis of malhamensilipin A (3) and diastereoisomeric analogues from (E)-2-undecenal. The convergent synthesis relied upon iterative epoxidation and phosphorus(V)-mediated deoxydichlorination reactions as well a titanium-mediated epoxide-opening to construct the C11-C16 stereohexad. The latter transformation occurred with very high levels of stereoretention regardless of the C13 configuration of the parent epoxide, implicating anchimeric assistance of either the γ- or δ-chlorine atoms, and the formation of chloretanium or chlorolanium ions, respectively. A computational analysis of the chloronium ion intermediates provided support for the involvement of chlorolanium ions, whereas the potential chloretanium ions were found to be less likely intermediates on the basis of their greater carbocationic character Royal Society of Chemistry 2016-08-02 Article PeerReviewed Saska, J., Lewis, W., Paton, R.S. and Denton, R.M. (2016) Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions. Chemical Science . ISSN 2041-6539 http://pubs.rsc.org/en/content/articlelanding/2016/sc/c6sc03012b#!divAbstract doi:10.1039/C6SC03012B doi:10.1039/C6SC03012B |
| spellingShingle | Saska, J. Lewis, W. Paton, R.S. Denton, R.M. Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title | Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title_full | Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title_fullStr | Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title_full_unstemmed | Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title_short | Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| title_sort | synthesis of malhamensilipin a exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions |
| url | https://eprints.nottingham.ac.uk/35946/ https://eprints.nottingham.ac.uk/35946/ https://eprints.nottingham.ac.uk/35946/ |